Tensio-active polypod compounds, process for preparing them and compositions containing them

ABSTRACT

Tensio-active cyclic polyethers of the general formula: ##STR1## where A refers to a hydrophile block chosen from the amine, ammonium, ammonio alkyl carboxylate, ammonio alkyl sulfonate, amide, sulfonamide, ether, thioether, hydroxyl, ester and acid groupings. 
     These polyethers may be prepared (1) by reaction of alcohol or of undecylenic acid with thioacetic acid, (2) saponification with an alkaline base, (3) reaction of the product obtained in (2) with the tetramer of epichlorohydrin or of epibromohydrin, (4) reaction of mesylate or tosylate of the compound obtained in (3) either (a) with dimethylamine or methylethanolamine, the resulting compound being able to be salified or alkylated, or (b) with the mercapto ethanol or mercapto glycerol; the compounds thereby obtained being then able to be submitted to reactions of polyaddition of ethylene oxide and/or of glycidol oxide. 
     These tensio-active cyclic polyethers are suitable for use in the cosmetic, textile, insecticide and similar industries.

This is a divisional of application Ser. No. 266,992 filed May 26, 1981,now U.S. Pat. No. 4,362,714 which in turn is a divisional of applicationSer. No. 56,204, filed July 10, 1979, now U.S. Pat. No. 4,290,956.

The invention relates to new tensio-active cyclic polyethers, called"Polypods", the processes for preparing same and the compositionscontaining same.

The new tensio-active cyclic polyethers possess remarkablecharacteristics which set them apart from similar compounds previouslydescribed. By their chemical structure, they are somewhat similar toCrown ethers, which have been very much studied, these last few years ascomplexing agents of cations of alkaline metals or alkaline earthmetals.

They are different in regard to their amphiphile character, i.e., anaffinity at the same time for water and for organic media, which givesthem a strong interfacial activity.

They are also distinguished from conventional surface-active agents,which include a single lipophile chain per molecule.

As is well known, the latter, when they are dissolved in water,show--beyond a threshold of concentration called critical micellarconcentration--a body of properties which are very advantageous for alarge number of applications. In particular, at concentrations at leastequal to this threshold, they dissolve in water organic substances, suchas liposoluble dyes and hydrocarbides.

The compounds according to the invention possess dissolving propertiesat very weak concentrations, often quite a bit lower than the criticalmicellar concentration of surface-active agents which have one lipophilechain of comparable length.

This is an important advantage for certain uses of tensio-actives, suchas, e.g., in pharmaceutical or cosmetic compositions, where there is aninterest in reducing as much as possible the quantity of tensio-activecompound used in order to not interfere with the active principle ofthese compositions.

In addition, the compounds of the invention are less aggressive to skinand to mucous membranes, especially to ocular membranes, or less"denaturing" to proteins, than the surface-active agents having onesingle lipophile chain per molecule and comparable functional groupings.

The new tensio-active cyclic polyethers, called "Polypods", may berepresented by the general formula: ##STR2##

This general formula may also be written in a simplified form: ##STR3##

In formulas (I) and (Ia), A refers to a hydrophile block which is linkedto the cycle by the thia-11 dodecamethylene radical which composes thelipophile ensemble.

The molecular configuration of the compounds of the invention resemblesthe form of certain invertebrates possessing several tentacles, whencethe name of "Polypods" used here in order to refer to them, which hasbeen proposed for similar compounds by R. Fornasier & F. Montanari,"Tetrahydronic Letters" No. 17, pp. 1381-1384 (1976).

The hydrophile block A, may be cationic, zwitterionic, anionic ornon-ionic. It may contain one or several identical or differentgroupings, selected from the group consisting of amine, ammonium,ammonio alkyl carboxylate, ammonio alkyl sulfonate, amide, sulfonamide,ether, thioether, hydroxyl, ester and acid groupings.

The ionic or non-ionic hydrophil block A, may be chosen from one of thefollowing groups: ##STR4## where R₁ refers to CH₃ or --CH₂ --CH₂--O]_(n) H,

n refers to a whole or decimal number from 1 to 10; ##STR5## where

V.sup.⊖ refers to the anion of an organic or mineral acid and preferablya chloride, bromide, sulfate, phosphate, acetate, glycolate, lactate,tartrate, methane sulfonate, or paratoluene sulfonate anion,

R₁ has the meaning indicated in (a); ##STR6## where R₂ refers to analkyl or hydroxyalkyl radical having from 1 to 3 carbon atoms andpreferably a methyl, hydroxyethyl or dihydroxypropyl radical,

X.sup.⊖ refers to an anion and preferably a chloride, bromide, iodide,methyl sulfate, mesylate or tosylate anion,

R₁ has the meaning indicated in (a); ##STR7## where

Q.sup.⊖ refers to one of the groupings

    --CH.sub.2 COO.sup.⊖

    --CH.sub.2 --CH.sub.2 COO.sup.⊖

    --CH.sub.2 --CH.sub.2 --CH.sub.2 --SO.sub.3.sup.⊖,

R₁ has the meaning indicated in (a);

    --(CH.sub.2 --S--CH.sub.2).sub.w --CONH--(CH.sub.2).sub.m --B (e)

where

m refers to the number 2 or 3,

w refers to the number 0 or 1,

B refers to one of the groupings: ##STR8##

Q.sup.⊖ has the meaning indicated in (d),

R₂ and X.sup.⊖ have the meaning indicated in (c),

V.sup.⊖ has the meaning indicated in (b); ##STR9##

n having the meaning indicated in (a),

w refers to the number 0 and 1,

B having the meanings indicated in (e);

    --CH.sub.2 --S--CH.sub.2 ].sub.w COO M.sub.1               (g)

M₁ refers to an ammonium or an alkaline metal, such as lithium, sodiumor potassium,

w refers to the number 0 or 1;

    --CH.sub.2 --O--SO.sub.3 M                                 (h)

M refers to a hydrogen atom, ammonium or an alkali metal such aslithium, sodium or potassium;

    --CH.sub.2 --S--Y--O].sub.n H                              (i)

Y refers to the ethylene or hydroxypropylene radical,

n refers to a whole or decimal number from 1 to 10; ##STR10##

p and g, identical or different, refer to a whole or decimal number from1 to 10,

however, p and g do not refer simultaneously to zero,

Y has the meaning shown in (i),

Z may refer to one of the following groupings: ##STR11## where

R₁ has the meaning shown in (a),

V.sup.⊖ has the meaning shown in (b),

R₂ and X.sup.⊖ have the meaning shown in (c),

Q.sup.⊖ has the meaning shown in (d),

M has the meaning shown in (h),

and, in addition, when p refers to zero or when Y refers to the ethylenegrouping, Z may refer to one of the groupings:

    --OSO.sub.3 M or --OCO--CH.sub.2 --SO.sub.3 M,

M having the above meaning.

The distribution of the units: ##STR12## is most generally adistribution in blocks, as shown in formula (j). However, when Y refersto the hydroxypropylene grouping, the distribution may also bestatistical.

The compounds of formula (I) may be prepared from undecylenic alcohol orundecylenic acid.

By reaction of these compounds with thioacetic acid followed bysaponification with an alkaline base and preferably with sodiumhydroxide or potassium hydroxide, one obtains, respectively:

mercapto-11 undecanol-1 of the formula

    HS--(CH.sub.2).sub.10 --CH.sub.2 OH                        (II)

or mercapto-11 undecanoic-1 acid of the formula

    HS--(CH.sub.2).sub.10 --COOH                               (III)

The preparation of these intermediary compounds of formulas (II) and(III) is described more in detail in Examples 1 and 2.

By reacting mercapto-11 undecanol-1 with the tetramer of epichlorohydrinor of epibromohydrin of formula (IV) ##STR13## which, in simplifiedform, is written: ##STR14## where Hal refers to chloride or bromide, oneobtains the intermediary compound of formula (V) ##STR15## whosepreparation is described in more detail in following Example 4.

Through reaction, either of mercapto-11 undecanoic-1 acid, or of itsmethylic or ethylic ester with the tetramer of epichlorohydrin or ofepibromohydrin of formula (IV), or of methyl thioglycolate or of ethylthioglycolate with the halogenate derivative, mesylate or tosylate ofthe compound of formula (V), one obtains the intermediary compound (VI):##STR16## where

R refers to hydrogen, CH₃ or C₂ H₅,

w refers to the number 0 or 1.

The invention also relates to the intermediary compounds of formula(VII): ##STR17## where R₃ refers to: --CH₂ OH, --CH₂ --O--SO₂ --CH₃,--CH₂ --O--SO₂ --C₆ H₄ --CH₃ --COOH, --COOCH₃, --COOC₂ H₅, --CH₂--S--CH₂ --COOH, --CH₂ --S--CH₂ --COOCH₃ or --CH₂ --S--CH₂ --COOC₂ H₅.

The tetramer of epichlorohydrin or of epibromohydrin of formula (IV) isprepared by polymerization of epichlorohydrin or of epibromohydrin inthe presence of a Lewis acid catalyst, such as BF₃, SnCl₄, SbCl₅ ortheir mixture and purified by fractionation under reduced pressure. Thisprocess is described in Example 3.

The compounds of type I(a), responding to formula (I) in which A refersto grouping (a), are prepared by the reaction of dimethylamine ormethylethanolamine,

either with the chlorinated or brominated derivative of the intermediarycompound of formula (V) (obtained by reacting the compound of formula(V) with, respectively, chloride of thionyl or hydrobromic acid),

or with the mesylate or tosylate of this compound of formula (V).

The condensation of the amine may be carried out at atmospheric pressureor in an autoclave, at a temperature between 20° and 160° C. When oneuses methylethanolamine, the compound obtained may possibly beoxyethylenated with ethylene oxide, and preferably with 1 to 10 molesethylene oxide by mole by compound (I).

The compounds of type I(b), responding to formula (I) in which A refersto grouping (b), are derived from compounds I(a) by salification with amineral or organic acid, and advantageously with one of the followingacids: hydrochloric, hydrobromic, sulfuric, phosphoric, acetic,glycolic, lactic, tartaric, methane sulfonic, paratoluene sulfonic.

The compounds of type I(c), responding to formula (I) in which A refersto the grouping (c), may be prepared by the alkylation of compounds I(a)with an alkylating agent, such as chloride, bromide, iodide, mesylate ortosylate of methyl, dimethyl sulfate, glycol chlorohydrin or glycerolchlorohydrin.

The compounds of type I(c), in which X.sup.⊖ refers to a mesylate anion(methane sulfonate) or tosylate (p-toluene sulfonate), may also beobtained by the reaction of mesylate or tosylate of the intermediarycompound of formula (V) with an amine of the formula: ##STR18## where

R₁ refers to CH₃ or --CH₂ --CH₂ --]_(n) H,

n refers to a whole or decimal number from 1 to 10,

R₂ refers to a methyl radical, hydroxyethyl or dihydroxypropyl radicalat a temperature of from 20° to 100° C.

The compounds of type I(d), responding to formula (I) in which A refersto the grouping (d), may be prepared by the alkylation of compounds I(a)with chloracetate or chloropropionate of sodium or propane sultone, at atemperature of from 10° to 100° C.

The compounds of the type I(e), responding to formula (I) in which Arefers to the grouping (e), may be prepared by the condensation of theintermediary compound of formula (VI) with a primary-tertiary diamine,such as dimethylamino ethylamine or dimethylamino propylamine.

The condensation of primary-tertiary diamine is carried out at atemperature of from 20° to 160° C.

The amine groupings of the amino amides thus obtained may then becombined in a salt with a mineral or organic acid as indicated forcompounds of type I(b). They may also be alkylated with alkylatingagents, such as those indicated for compounds of type I(c) and I(d).

The compounds of type I(f), responding to formula (I) in which A refersto grouping (f), are obtained by the condensation of the intermediarycompound of formula (VI) with an oxyethylenated dimethylamine of theformula ##STR19## where n refers to a whole or decimal number from 1 to10; the condensation is carried out at a temperature of from 20° to 160°C.; the amine groupings may then be combined in a salt with a mineral ororganic acid or alkylated with an alkylating agent.

Compounds of the type I(g), responding to formula (I) in which A refersto grouping (g), are obtained by saponification of the methylic orethylic ester of the intermediary compound of formula (VI), followed byneutralization with an alkaline or ammoniac hydroxide or, when w refersto zero, directly by reaction at a temperature of from 60° to 130° C. ofthe epichlorohydrin or epibromohydrin tetramer with the mercapto-11undecanoic-1 acid in the presence of sodium or potassium methylate orethylate, followed by neutralization with an alkaline hydroxide orammoniac hydroxide.

The compounds of type I(h), responding to formula (I) in which A refersto the grouping (h), are obtained by sulfating of the intermediarycompound of formula (V) with sulfuric chlorohydrin at a temperature offrom 0° to 80° C. and possible neutralization with an alkaline orammoniac hydroxide.

These reactions may be carried out without a solvent or in the presenceof a solvent, such as chloroform, benzene, toluene, ether, glycolethers.

The compounds of type I(i), responding to formula (I) in which A refersto grouping (i), are obtained by reaction of mercapto-ethanol or ofmercaptoglycerol with mesylate or tosylate of the intermediary compoundof formula (V) or with a halogenated compound derived from that one.These reactions are generally carried out in a solvent (preferablyethanol, propanol, isopropanol, t-butanol, butanol-1, glycols ormonoethers of glycol, with possibly water) in the presence of methylateor ethylate of sodium or potassium, or sodium or potassium hydroxide, attemperatures between 60° and 160° C.

The derivatives thereby obtained may then initiate reactions ofpolyaddition of ethylene oxide and/or glycidol at 120° to 180° C. in thepresence of an alkaline catlyst, advantageously in the presence ofmethylate or ethylate of sodium or of potassium. Advantageously they maybe condensed with 1 to 10 moles of ethylene oxide and/or glycidol. Inthe case of addition at the same time of ethylene and of glycidol, theseadditions are generally carried out in two successive stages, the orderof the additions being of no importance. These additions may be carriedout with or without solvent. The preferred solvents are: water,isopropanol, tertiobutanol, methyl ethyl ketone, methyl isobutyl ketone.

The compounds of the type I(j), responding to the formula (I) in which Arefers to the grouping (j), are obtained, in one or several stages, bypolyaddition of epoxydes with the intermediary compound of formula (V).

Useful epoxides are ethylene oxide, tertiobutyl glycidylether (TBGE), anephalohydrin, such as epichlorohydrin or epibromohydrin, and theirmixtures.

The reactions of polyaddition are generally sequential operations but,in the case where one uses TBGE and an epihalohydrin, one may also addthe two reagents simultaneously or in a mixture.

In the case of addition of TBGE to the intermediary compound of formula(V), the protector tertio-butoxy groupings may be replaced by hydroxylgroupings by heating at 50° to 120° C. in the presence of asulfocarboxylic or sulfonic acid. This reaction is described more indetail in French Pat. No. 2,027,585 and U.S. Pat. Nos. 3,840,606 and3,959,390 of the petitioner the disclosure of which is herebyincorporated by reference.

The halogen atoms of the oligomers obtained by reaction with anepihalohydrin may be replaced by a hydroxyl, thiohydroxyethyl,thiodihydroxypropyl, thioglycolate, amine, ammonium, ammonio acetate,ammonio propionate, ammonio propane sulfonate, or sulfonate grouping.

The replacement of halogen atoms by hydroxyl groupings is carried out byreaction with an alkaline salt of carboxylic acid and preferably withsodium or potassium acetate at a temperature of 150° to 200° C. in anappropriate solvent chosen advantageously from the glycols and thederivatives of glycol; the acetic ester formed is then cut bysaponification by means of sodium hydroxide or potassium hydroxide or byalcoholysis by means of an inferior alcohol and preferably by means ofmethanol or ethanol in the presence of a basic catalyst chosenpreferably from methylate or ethylate of sodium or of potassium.

The replacement of halogen atoms by a thiohydroxyethyl,thiodihydroxypropyl or thioglycolate grouping is carried out by reactionwith thioethanol, thioglycerol or thioglycolate of methyl or ethyl, at atemperature of 20° to 150° C., in the presence possibly of a solvent andof an alkaline compound chosen advantageously from hydroxide, methylateand ethylate of sodium or potassium.

The replacement of halogen atoms by amine groupings is carried out asfor the compounds of type I(a).

The invention also relates to compositions comprising at least onetensio-active cyclic polyether of formula (I).

Among these compositions, it is necessary to mention more particularlythe cosmetic and pharmaceutical compositions comprising at least0.5×10⁻² gram per liter or 0.5×10⁻³ % in weight of a tensio-activecyclic polyether of formula (I) or of a mixture of them.

The cosmetic compositions include notably the compositions designed forskin, nails, and hair care.

The compositions for hair care aim notably at shampoos and conditionersfor the hair, as well as dyeing compositions and colouring shampoos.

The cosmetic compositions may be in the form of an aqueous orhydroalcoholic solution, or in the form of a cream, a gel, an emulsionor an aerosol.

The hydroalcoholic solutions include generally an alcohol or a polyolhaving from 1 to 4 carbon atoms and preferably ethanol or isopropanol,advantageously in a proportion of 5 to 70% of the total weight of thecomposition.

The cosmetic compositions for the treatment of the hair, and inparticular shampoos, colouring shampoos and hair dye compositions, mayalso contain in addition to a tensio-active cyclic polyether of formula(I) an adjuvant chosen from from the group consisting of the anionic,cationic, amphoteric, zwitterionic or non-ionic surface-active agentsand their mixtures, perfumes, dyes, preservatives, foam synergists, foamstabilizers, softening agents, agents for restructuring hair,anti-dandruff agents, cosmetic resins, sequestrants, thickeners,electrolytes and cosmetic polymers.

Colouring shampoos and hair dye compositions, in addition, contain oneor several direct dyes and, in particular, anthraquinionic dyes, azoicdyes, nitrated dyes of the benzene series, indophenols, indoanilines,indamines.

The pH of the compositions is generally between 3 and 11

The invention also relates to a process for treatment of hair consistingof the application to the hair of an effective amount of an aqueous orhydroalcoholic composition including one or several tensio-active cyclicpolyethers of formula (I) and possibly one or several adjuvants definedabove.

The invention will be better understood with the help of thenon-limiting examples which follow.

EXAMPLE 1 Preparation of mercapto-11 undecanol-1 [intermediary compoundof formula (II)]

To 256 g (1.5 mole) of undecylenic alcohol, 3.7 g ofazodiisobutyronitrile is added; then in the space of one hour, 105.5 g(1.5 mole) of thioacetic acid is added, while keeping the temperaturebetween 25° and 50° C. The product is heated to 70° C. for 4 hours, andone obtains the compound:

    CH.sub.3 --CO--S--(CH.sub.2).sub.10 --CH.sub.2 OH

The rate of reaction determined by titration of the SH grouping is 95%.

The reactive mass is mixed with 200 ml of ethanol at 96° C. and 40 ml ofwater. The mass is saponified by adding 165 g of aqueous solution ofsodium hydroxide at 10 meq/g (milliequivalent per gram) and heating for1 hour at the temperature of reflux. The product is acidified withchlorohydric acid and the organic phase is separated by decantation andwashed three times with 300 ml of water at 80° to 90° C.

After dehydration, the mercapto-11 undecanol-1 is distilled at 126° to130° C. under pressure of 0.4 mm of Hg.

The product obtained is in the form of a white solid having a SH indexof 4.8 meq/g.

EXAMPLE 2 Preparation of the mercapto-11 undecanoic-1 acid [intermediarycompound of formula (III)]

To 184 g (1 mole) of undecylenic acid, 2.5 g of azodiisobutyronitrile isadded; then in 40 minutes, 76 g (1 mole) of thioacetic acid is added.The reaction is exothermic and the temperature rises from 24° to 65° C.The product is heated to 70° C. for 3 hours. The compound of thefollowing formula is obtained:

    CH.sub.3 --CO--S--(CH.sub.2).sub.10 --COOH

The rate of reaction according to titration of the --SH grouping is98-99%.

The reactive mass is diluted with 100 g of ethanol at 96° C. Then 220 g(2.2 moles) of aqueous soluton of sodium hydroxide at 10 meq/g is addedover 30 minutes. After being heated for 1 hour at 70° C., the product isacidified with 190 ml of concentrated hydrochloric acid.

The mercapto-11 undecanoic-1 acid is decanted and then washed four timeswith 100 ml of water at 65° to 70° C. It is then dried by heating underreduced pressure and distilled at 145° C. under a pressure of 0.07 mmHg.

Acid index=4.38 meq/g

SH index=4.28 meq/g

EXAMPLE 3 Preparation of the tetramer of epichlorohydrin [intermediarycompound of formula (IV)] by polymerization of epichlorohydrin ##STR20##

In a reactor of 61, 1180 g of epichlorohydrin and 500 ml of carbontetrachloride are mixed. The mixture is chilled to 10° C. by immersionin an ice bath. Under energic agitation, 16 g of etherate of trifluorideof boron in solution in 1 liter of carbon tetrachloride is added in 6hours. One keeps the temperature during this time between 10° and 13° C.

The temperature is allowed to rise and the mixture is progressivelycarried to the temperature of reflux during 1 hour. 50 g of dry andfinely pulverized sodium carbonate is added and agitated for 2 hours atreflux. The mineral salts are then separated by filtration. The carbontetrachloride is evaporated under reduced pressure, then onefractionates by distillation.

Thus, there is obtained, at 185° C. and under pressure of 0.2 mm of Hg,210 g of product which is present in the form of a colorless vitreousmass crystalizing at the end of several days. Titration of organicchlorine: 10.6 meq/g.

EXAMPLE 4 Preparation of intermediary compound of formula (V) ##STR21##

74 g (0.8 equivalent in chlorine) of epichlorohydrin tetramer and 167 g(0.8 mole) of compound of formula (II) are dissolved in 600 ml ofabsolute ethanol. 152 g (0.82 mole) of sodium methylate in methanol, at5.4 meq/g is added drop by drop at 40° C. in 30 minutes.

After 7 hours of heating at reflux, the rate of reaction is 96%.

The residual alkalinity is possibly neutralized with concentrated HCl.Then the sodium chloride formed is separated by filtration.

After elimination of ethanol by distillation, a solid compound whoseindex of thioether is 3.75 meq/g and the index of hydroxyl is 4.1 meq/gis obtained.

EXAMPLE 5 Preparation of the intermediary compound ##STR22## [sulfonicmethane ester of compound (V) prepared in Example 4 ]

180 g of compound (V), (0.7 theoretical equivalent in hydroxyl grouping)is dissolved in 300 ml of anhydrous benzene. 71.5 g of triethylamine(0.7 mole) is added and then, at the temperature of 15° C. and in 30minutes, 80 g (0.7 mole) of methane sulfochloride is added. The productis maintained under agitation for 2 hours between 15° and 20° C.

The triethylamine chlorohydrate is filtered and washed twice with 200 mlof benzene.

The benzenic phase is extracted with water and then dried on sodiumsulfate.

After elimination of the solvent, the compound of formula (VIII) isobtained in the form of a clear yellow oil whose index of saponificationis 3.08 meq/g.

EXAMPLE 6 Preparation of the intermediary compound: ##STR23##

To 34 g (100 meq) of intermediary compound of formula (VIII), preparedaccording to Example 5, dispersed in 100 g of absolute ethanol, 12.3 g(0.1 mole) of ethyl thioglycolate and 18.6 g (0.1 mole) of sodiummethylate in methanol, at 5.4 meq/g are added (at the surroundingtemperature).

The solution is heated for 7 hours at reflux. The methane sodiumsulfonate formed thereby is filtered. The solvent is eliminated underreduced pressure.

The compound of formula (IX) in the form of a clear brown oil isobtained which has the following characteristics: Index ofsaponification: 2.7 meq/g

S%: 17.7

EXAMPLE 7 Preparation of a compound of formula (I) in which A refers tothe grouping: ##STR24##

43 g (0.13 equivalent) of intermediary compound of formula (VIII),prepared in Example 5 is dissolved in 150 g of benzene, 120 ml ofbenzenic solution of dimethylamine at 33% is added in 20 minutes and atordinary temperature.

After 5 hours of agitation at 40° C., the reaction rate calculatedaccording to the acid index appearing is practically quantitative.

The excess amine and the solvent are eliminated under reduced pressure,after neutralization of the methane sulfonic acid formed thereby, withsodium methylate. The reactive mass is dissolved in 250 ml of chloroformand extracted three times with 60 ml of water.

After drying, a clear brown oil containing 11.5% of S and 4.74% ofnitrogen is obtained.

This oil is soluble in water after neutralization with an acid, forexample, lactic acid or chlorohydric acid.

EXAMPLE 8 Preparation of a compound of formula (I) in which A refers tothe grouping: ##STR25##

To 33.8 g (100 meq) of intermediary compound of formula (VIII) preparedaccording to Example 5, 16 g (0.2 mole) of methylethanolamine is addedat 45° C. and in 10 minutes. After 8 to 9 hours at 80° C., the reactionis practically quantitative.

The reactive mass is taken up with 100 ml of isopropanol and 16.3 g ofsodium methylate in methanol, at 5.4 meq/g is added. The sodium methanesulfonate is filtered out and the solvent and the excess amine areeliminated by distillation under reduced pressure.

The residue is taken up in chloroform and the organic phase is washed inwater.

A clear brown thick oil soluble in a diluted acid medium and having thefollowing characteristics is obtained:

S%=10.1

N%=4.42

EXAMPLE 9 Preparation of a compound of formula (I) in which A refers tothe grouping: ##STR26##

To 13.5 g (40 meq) of intermediary compound of formula (VIII) preparedaccording to Example 5, 3.63 g (0.04 mole) of dimethyl ethanolamine isadded and heated for 3 hours at 60° C.

A clear yellow paste soluble in water is obtained. S%=15.63-15.89.

EXAMPLE 10 Preparation of a compound of formula (I) in which A refers tothe grouping: ##STR27##

To 5.75 g (0.20 equivalent of amine) of compound prepared according toExample 7, 2.45 g (0.020 mole) of chloracetate of ethyl is added atordinary temperature.

The product is heated for 1 hour at 50° C.

The rate of reaction, calculated according to the index of remainingbasicity, is practically quantitative.

20 ml of ethanol is added to the reactive medium; then 20 meq of NaOH insolution in 10 ml of water is added. After 35 minutes of heating toreflux, the product is neutralized by addition of 2 ml of concentratedhydrochloric acid.

After elimination of sodium chloride and solvents, the product is takenup with 20 ml of dimethylether of diethyleneglycol.

A white powder soluble in water, having a melting point of 150° C. andcontaining 3.2% nitrogen and 8.6% sulfur is thereby obtained.

EXAMPLE 11 Preparation of a compound of formula (I) in which A refers tothe grouping: ##STR28##

To 5.5 g (15.2 meq) of intermediary compound of formula (IX), preparedaccording to Example 6, 0.1 g (0.5 meq) of sodium methylate in methanoland 3.5 g (30 meq) of dimethyl aminopropylamine are added.

The reactive medium is heated for 15 hours at 110° C.

The reactive mass is dissolved in 20 ml of chloroform and washed threetimes with 10 ml of water. The organic phase is then dried on sodiumsulfate, then heated under reduced pressure to eliminate the ethanolthereby formed and the methanol used as a solvent.

The desired compound is in the form of a paste of clear brown color,soluble in water in the presence of an acid, for example, hydrochloricor lactic acid.

The compound obtained possesses the following characteristics:

Index of basicity: 2.5 meq/g

N%: 15.14

S%: 6.57

EXAMPLE 12 Preparation of a compound of formula (I) in which A refers tothe grouping:

    --COOH--                                                   (g)

In 600 g of absolute ethanol, 22.3 g (0.24 equivalent in chlorine) ofepichlorohydrin tetramer and 55.2 g (0.24 mole) of mercapto-11undecanoic-1 acid are dissolved. Then, in 45 minutes, 96 g (0.48 mole)of sodium methylate in methanol is added. The reactive mass is heatedfor 5 hours at 50° C., and then 3 hours to reflux.

The product is acidified by the addition of concentrated hydrochloricacid. The acidified product is diluted with warm water. The organicphase is separated by decantation at 80° C., and washed and dried underreduced pressure.

Thus, there is obtained the desired compound in the form of a whitesolid with a melting point of 60° C., acid index 3.49 meq/g, and whichis soluble in water, in the form of an alkaline salt or an amine salt,for example, sodium salt, potassium or triethanolamine salt.

EXAMPLE 13 Preparation of a compound of formula (I) in which A refers tothe grouping:

    --CH.sub.2 --S--CH.sub.2 --COOH                            (g)

To 18.1 g (0.05 equivalent) of compound of formula (IX) prepared inExample 6, dissolved in 200 ml of ethanol at 96° C., 6 g of aqueoussolution of NaOH at 10 meq/g and 20 ml of water are added. The mixtureis heated for 1 hour to reflux.

200 ml of water is added. After acidification with HCl, thecorresponding acid is extracted with chloroform.

After drying under reduced pressure, the desired compound is obtained inthe form of a clear yellow solid, soluble in water, in the form of analkaline salt or an amine salt, for example in the form of sodium salt,potassium salt, or triethanolamine salt.

The characteristics of this compound are as follows:

Acid index: 2.7 meq/g

S%: 19.1

EXAMPLE 14 Preparation of a compound of formula (I) in which A refers tothe grouping:

    --CH.sub.2 --S--CH.sub.2 --CHOH--CH.sub.2 OH               (i)

To 17 g (50 meq) of intermediary compound of formula (VIII), preparedaccording to Example 5, dispersed in 20 g of absolute ethanol, 6 g(0.050 mole) of thioglycerol in 10 g of absolute ethanol is added. 13.5g of sodium methylate in methanol, at 3.7 meq/g is then added.

The reaction mass is heated to reflux during 7 hours.

The methane sodium sulfonate thereby formed is separated by filtrationand the solvent is eliminated under reduced pressure.

The desired compound so obtained possesses the followingcharacteristics:

OH Index: 5.8 meq/g

S%: 17.5

EXAMPLE 15 Preparation of a compound of formula (I) in which A refers tothe grouping:

    --CH.sub.2 --S--CH.sub.2 --CHOH--CH.sub.2 ]H               (i)

To 7 g (0.020 equivalent in hydroxyl grouping) of compound preparedaccording to Example 14, 0.35 g of sodium methylate is added; then, inthe space of 1 hour, at a temperature of 150° C., 7.65 g (0.1 mole) ofglycidol is added.

The desired compound thus obtained is in the form of a clear brown pastesoluble in water.

Cloud point in salted water containing 25 weight percent NaCl: 88° C.

EXAMPLE 16 Preparation of a compound of formula (I) in which A refers tothe grouping:

    --CH.sub.2 --OSO.sub.3 M                                   (h)

where M refers to H or NH₄ or HN(CH₂ --CH₂ OH)₃.

(a) Preparation of the acid (M=H)

5.2 g (0.02 equivalent in hydroxyl grouping) of intermediary compound offormula (V) are put into solution in 10 ml of chloroform. In the spaceof 10 minutes. 2.33 g of sulfuric chlorohydrin in solution in 5 ml ofchloroform is added. The temperature rises from 20° to 30° C; aigtationis maintained for 20 minutes.

After elimination of the chloroform under reduced pressure, a clearyellow oil is obtained.

(b) Preparation of ammonium salt (M=NH₄)

The acid thereby obtained is put into solution in 10 ml of ethanol at90° C. Under agitation 6 ml of 6N ammoniac is added. Afterconcentration, the reaction mass is taken up with 2 ml of absoluteethanol and 10 ml of ether; then the ammonium salt is succion filteredthen washed with 5 ml of ether. It is in the form of a wite powdersoluble in warm water. By recooling, the aqueous solution gels to form atranslucid mass.

(c) Preparation of triethanolamine salt [M=HN(CH₂ --CH₂ OH)₃ ]

To the acid put in solution in 10 ml of ethanol at 90° C., 3 g oftriethanolamine in solution in 10 ml of ethanol at 90° C. is added. Thesolvent is eliminated by distillation under reduced pressure. Theproduct is in the form of a clear yellow paste, soluble in warm water,giving an opalescence when cool.

EXAMPLE 17 Preparation of a mixture of compounds of formula (I) in whichA refers to the grouping: ##STR29## [grouping of type (f) in which w=1and n=5.5]

18.07 g (0.05 equivalent in ester grouping) of intermediary product offormula (IX) are mixed with 17.3 g of oxyethylenated N,N-diethylaminoethanol (0.05 mole).

Under agitation, 1 g of sodium methylate in methanolic solution at 30%is added. The temperature is raised to 110° C. while eliminating theethanol at ordinary pressure, then under reduced pressure for 1 hour 30minutes.

The product thereby obtained is in the form of a brown oil, verydispersible in water, soluble in acetic acid or in diluted lactic acid.

Basicity index: 1.6 meq/g

EXAMPLE 18 Preparation of the mixture of compounds of formula (I) inwhich A refers to the grouping: ##STR30## p=q=2 To 13 g (0.05 equivalentin hydroxyl grouping) of intermediary compound of formula (V) melted,0.1 ml of BF₃ complex in ether and 1 g of dry zinc chloride are added.The mixcture of 13 g of tertiobutylglycidylether (0.1 mole) and 9.25 gepichlorohydri (0.1 mole) is introduced under agitation for 20 minutes.It is heated for 8 hours at 105° C. under agitation. Then, 0.25 g ofsulfoacetic acid is added and the mixture is heated at 100° C. underagitation until the end of gaseous release. Duration of the reaction:about 8 hours.

The reactive mass is taken up again with 40 ml of dichloroethane and thesolution is washed with 40 ml of water saturated with sodiumbicarbonate, then with 40 ml of water. The organic phase is dried onanhydrous sodium sulfate and concentrated dry.

15.1 g of the so-obtained product is put in solution in 50 ml ofabsolute ethanol. 6.95 g of thioglycerol is added, the mixture beingheated at 45° C.

Under agitation, 9.5 g of methanolic solution of sodium methylate at 6.1meq/g is added.

The reactive medium is maintained for 8 hours at reflux. The reaction isfollowed by titration of the mercaptan function. The sodium chloridethereby formed is separated by filtration and the filtrate concentrateddry under reduced pressure.

One obtains a thick brown oil, dispersible in water.

Cloud point measured at a concentration of 5% in an aqueous solutioncontaining 25% butyldiglycol at 79° C.

EXAMPLE 19

The following coloring lotion is prepared:

    ______________________________________                                        Compound of Example 14     1      g                                           1-[N(3-aminopropyl)amino]anthraquinone                                                                   0.05   g                                           Water q.s.p.               100    g                                           ______________________________________                                    

This solution, applied during 30 minutes on bleached hair, gives them,after rinsing, shampooing and rinsing, a clear rose salmon tint.

EXAMPLE 20

The following coloring lotion is prepared:

    ______________________________________                                        Compound of Example 9      1.2    g                                           4-[N--(beta-hydroxyethyl)]aminophenyl-                                                                   0.1    g                                           azo-4-nitrophenyl                                                             Water q.s.p.               100    g                                           ______________________________________                                    

This solution, applied during 30 minutes on bleached hair, gives them,after rinsing, shampooing and rinsing, a golden sable tint.

EXAMPLE 21

The following coloring lotion is prepared:

    ______________________________________                                        Salt of triethanolamine of the compound of Example 13                                                     1      g                                          1,4-bis-(methylamino)-2-nitro phenyl                                                                      0.08   g                                          Water q.s.p.                100    g                                          ______________________________________                                    

This lotion, applied during 30 minutes on bleached hair, gives them,after rinsing, shampooing and rinsing, a clear rose cyclamen tint.

EXAMPLE 22

An anionic shampoo of the following composition is prepared:

    ______________________________________                                        Compound of Example 7   0.6    g                                              Lauryl triethanolamine sulfate                                                                        6      g                                              Lauric diethanolamide   3      g                                              Lactic acid q.s.p.      pH     6                                              Water q.s.p.            100    g                                              ______________________________________                                    

EXAMPLE 23

A non-ionic shampoo of the following composition is prepared:

    ______________________________________                                        Compound of Example 8       0.8    g                                          Hydroxy alkyl ether of polyglycerol of the formula:                            ##STR31##                                                                    ______________________________________                                    

where R represents a mixture of alkyl radicals having from 9 to 12

    ______________________________________                                        carbon atoms          9      g                                                Lactic acid q.s.p.    pH     6.7                                              Water q.s.p.          100    g                                                ______________________________________                                    

The solutions of Examples 22 or 23 are applied to a head of hair inorder to soften all the soiled areas. The hair is rinsed and subjectedto a second application; a rich lather is obtained and then rinsed. Thedried hair separates easily and permits easy shaping or setting of thehair.

What is claimed is:
 1. Dye composition for the hair, said compositioncomprising water or a hydroalcoholic medium, a cosmetically effectivequantity of one or several compounds of the formula: ##STR32## wherein Arefers to a cationic, anionic, zwitterionic or non-ionic hydrophileblock which comprises one or more groupings, identical or different,selected from the group consisting of amine, ammonium, ammonio alkylcarboxylate, ammonio alkyl sulfonate, carboxylic amide, ether,thioether, hydroxyl, carboxylic ester and carboxylic acid grouping, anda dye for hair.
 2. Composition according to claim 1, characterized bythe fact that the dye is chosen from the anthraquinonic dyes, the azoicdyes, nitrated dyes of the benzenic series, indophenols, indoanilines,and indoamines.
 3. A composition according to claim 1 which is in theform of a cream, a gel, an emulsion or an aerosol, said compositionhaving no shampoo characteristics.
 4. A composition according to claim 1which further comprises at least one adjuvant selected from the groupconsisting of anionic, cationic, non-ionic, zwitterionic, amphoterictensio-actives and their mixtures, perfumes, preservatives, thickeners,softeners, cosmetic resins, and sequestrants, said adjuvant conferringno shampoo characteristics to said composition.